EP0314618B1 - Procédé pour la préparation de composés organométalliques - Google Patents

Procédé pour la préparation de composés organométalliques Download PDF

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EP0314618B1
EP0314618B1 EP88810710A EP88810710A EP0314618B1 EP 0314618 B1 EP0314618 B1 EP 0314618B1 EP 88810710 A EP88810710 A EP 88810710A EP 88810710 A EP88810710 A EP 88810710A EP 0314618 B1 EP0314618 B1 EP 0314618B1
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mol
ferrocene
process according
mixture
tetrahalide
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EP0314618A2 (fr
EP0314618A3 (en
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Vincent Dr. Desobry
Hans Oskar Dr. Doggweiler
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Ciba SC Holding AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to an improved process for the preparation of organometallic compounds, in particular iron-arene complexes, by ligand exchange reaction on ferrocene (derivatives).
  • Iron-arene complexes and their use as photoinitiators for cationically polymerizable materials are known and are described, for example, in EP-A 94,915.
  • the compounds are prepared from metallocene compounds by ligand exchange reactions.
  • the metallocene compound for example ferrocene, is reacted with an aromatic compound in the presence of a Lewis acid and Al metal.
  • the property of the Zr-IV or Hf-IV halide is used as an acceptor for the exchanged cyclopentadiene (derivative) and in the said cases an isolatable reaction product is obtained.
  • an isolatable reaction product is obtained.
  • ligand exchange with AlCl3 form from the outgoing cyclopentadiene (derivatives) usually polymeric products (see D. Astruc et al. in Tetrahedron, 32 , 245-249 (1976)).
  • the index q is preferably 1 or 2, particularly preferably 1.
  • R is an indenyl anion C9H7 or preferably a cyclopentadienyl anion C5H4R1.
  • R1 and R3 are straight-chain or branched as C1-C6-alkyl, preferably straight-chain. Examples of radicals of this type are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl or n-hexyl. Methyl is preferred.
  • R1 and R3 are halogen, fluorine, chlorine, bromine or iodine. Chlorine is preferred.
  • R1 and R3 are preferably hydrogen or methyl, very particularly preferably hydrogen.
  • Suitable ⁇ -arenes R2 are in particular aromatic hydrocarbons with 6 to 24 carbon atoms or heterocyclic-aromatic hydrocarbons with 3 to 30 carbon atoms and one or two heteroatoms, these groups optionally being substituted by identical or different monovalent radicals such as halogen atoms, preferably chlorine or Bromatome, or C1-C8-alkyl, C1-C8-alkoxy, cyano, C1-C8-alkylthio, C2-C6-carboxylic acid alkyl ester or phenyl groups can be mono- or polysubstituted.
  • halogen atoms preferably chlorine or Bromatome
  • C1-C8-alkyl, C1-C8-alkoxy, cyano, C1-C8-alkylthio, C2-C6-carboxylic acid alkyl ester or phenyl groups can be mono- or polysubstituted.
  • ⁇ -arene groups can represent mononuclear, condensed multinuclear or uncondensed multinuclear systems, the nuclei in the last-mentioned systems directly or via bridge members, for example via -CH2-, -CO-, -O-, -S- or -SO2-, can be linked.
  • Systems containing one or two S and / or O atoms are preferably suitable as heteroaromatic ⁇ -arenes.
  • Suitable ⁇ -arenes are benzene, toluene, xylenes, ethylbenzene, cumene, methoxybenzene, ethoxybenzene, dimethoxybenzene, p-chlorotoluene, m-chlorotoluene, chlorobenzene, bromobenzene, dichlorobenzene, diisopropylbenzene, trimethylbenzene, 1,2-naphthalenol, naphthalenol, naphthalene , 2,3,4-tetrahydronaphthalene, methylnaphthalene, methoxynaphthalene, ethoxynaphthalene, chloronaphthalene, bromnaphthalene, dimethylnaphthalene, biphenyl, stilbene, indene, 4,4′-dimethylbiphenyl, fluorene, phenanthrene, anthracene, 9,10
  • X can be any q-valent anion of an inorganic or organic acid.
  • halides that is to say fluoride, chloride, bromide and iodide, or pseudohalides, for example cyanide, cyanate or thiocyanate, or anions other inorganic acids, for example sulfate, phosphate, nitrate, perchlorate or tetraphenylborate.
  • Suitable anions are derived from sulfonic acids of aliphatic or aromatic compounds. Preferred examples of this are p-toluenesulfonate, p-trifluoromethylbenzenesulfonate or trifluoromethanesulfonate.
  • Non-nucleophilic anions X q ⁇ are particularly preferred.
  • Suitable non-nucleophilic anions X q ⁇ are in particular anions of the formula II [LQ m ] q ⁇ (II), wherein L is a divalent to seven-valent metal or non-metal, Q represents a halogen atom, preferably fluorine, or, in the event that L is phosphorus, arsenic or antimony and m 5, can additionally be OH, q is 1, 2 or 3 and m is an integer corresponding to the valence of L + q.
  • Examples of such anions are BF4 ⁇ , AlF4 ⁇ , AlCl4 ⁇ , TiF62 ⁇ , PF6 ⁇ , SbF6 ⁇ , SbCl6 ⁇ , SbF5 (OH) ⁇ , GeF6 ⁇ , ZrF62 ⁇ , AsF6 ⁇ , FeCl4 ⁇ , SnF62 ⁇ , SnCl62 ⁇ and BiCl6 ⁇ .
  • Preferred complex anions are BF4 ⁇ , and in particular AsF6 ⁇ , SbF6 ⁇ or PF6 ⁇ .
  • the Al trihalides or Zr-IV or Hf-IV tetrahalides defined above include the corresponding chlorides, bromides or iodides.
  • the chlorides or bromides are preferably used, but in particular the chlorides.
  • Preferred Zr-IV or Hf-IV tetrahalides are ZrBr4 or HfBr4 and in particular ZrCl4 or HfCl4.
  • Preferred Al trihalide is AlCl3, especially sublimed AlCl3.
  • the preferred total amount of Lewis acid in variant a) is 1.2-4.0 mol, in particular 1.6-2.0 mol, and very particularly preferably 1.7-1.9 mol, based on one mol of ferrocene (derivative ).
  • the preferred amount of Zr-IV or Hf-IV tetrahalide in variant b) is 1.0-3.0 mol, particularly preferably 1.5-2.0 mol, based on one mol of ferrocene (derivative).
  • the molar ratio of Zr-IV or Hf-IV tetrahalide to Al trihalide in variant a) is preferably 1: 4 to 4: 1, in particular 1: 2 to 1: 3.
  • Aluminum is particularly preferred.
  • the property of the Zr-IV or Hf-IV halide is used as a cyclopentadienyl acceptor.
  • the cyclopentadienyl (derivative) exchanged from the ferrocene (derivative) is thus transferred to the Zr-IV or Hf-IV halide.
  • a molar ratio of Al trihalide and the corresponding IV halide of 2: 1 or greater than 2: 1 is expediently chosen.
  • a mixture of 0.4-0.6 mol, preferably about 0.5 mol. ZrCl4 or HfCl4 and 1.2-1.4 mol, preferably 1.3-1.35 mol, is used , AlCl3. together with 0.15-0.2 moles of finely divided Al, based on one mole of ferrocene (derivative).
  • the metallic reducing agent is preferably added in an amount equivalent to the Zr-IV or Hf-IV tetrahalide.
  • the metallic reducing agent is preferably added in an amount equivalent to the Zr-IV or Hf-IV tetrahalide.
  • one third of the molar amount of the Zr-IV or Hf-IV tetrahalide is preferably used.
  • variant a) is carried out with an excess or a deficit of Zr-IV or Hf-IV tetrahalide, it is advisable to add a metallic reducing agent to increase the yields.
  • a metallic reducing agent to increase the yields. This can be used in any amount; however, more than 0.1 mol, particularly preferably 0.1-1.0 mol, based on one mol of ferrocene (derivative), should preferably be used.
  • a metallic reducing agent preferably Al metal
  • the metal should be used in a form that offers a large surface area.
  • it can be added as a film or in finely divided form, preferably as a powder or as dust.
  • the ⁇ -arene can be used in any excess, for example as a solvent. However, at least 1 mole, based on one mole of ferrocene (derivative), should be introduced. Mixtures of ⁇ -arenes can also be used.
  • the reaction is optionally carried out in a further solvent. All solvents which are inert under the reaction conditions can be used. The basicity of these solvents should not be too great in order not to deactivate the Lewis acid (s) excessively.
  • suitable solvents are (cyclo) aliphatic or aromatic hydrocarbons, which can optionally carry non-basic substituents, for example halogen atoms or alkyl groups. C6-C12 hydrocarbons are preferred.
  • Examples of preferred solvents of this type are n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane or corresponding branched representatives of these types; mixtures of aliphatic hydrocarbons can also be used, for example octane fraction.
  • the preferred cycloaliphatic solvent is methylcyclohexane.
  • the aliphatic hydrocarbons can optionally be chlorinated.
  • Other preferred solvents are benzene, toluene, xylene, ethylbenzene, cumene, chlorobenzene or dichlorobenzene.
  • the process is preferably carried out without additional solvent and the ⁇ -arene R2 is used in an amount of 2.0-10.0 mol, based on one mol of ferrocene (derivative).
  • the reaction mixture may optionally contain small amounts of water, for example 0.1-2% by weight, based on the amount of Lewis acid, as is the case when AlCl3 is used as Lewis acid in Koord. Khim., 1 , 1252 ( 1975).
  • the ferrocene is preferably ferrocene.
  • any derivatives which have substituted cyclopentadienyl anions or indenyl anions are bis-indenyl-iron (II), chloro- or dichlorferrocene or methyl- or dimethylferrocene.
  • Ferrocene or the easily accessible monosubstituted ferrocene derivatives are preferably used, but especially ferrocene.
  • the reaction is conveniently carried out in the temperature range of 15-250 ° C.
  • the preferred temperature range is 50-120 ° C.
  • reaction time is usually 0.25-24 hours. 1-2 hours are preferred.
  • the process can be carried out in air or under protective gas. It is advantageously carried out with the exclusion of oxygen, for example under nitrogen or under argon.
  • All of the starting materials can be initially introduced and the reaction can optionally be initiated by heating. In some cases, however, it may prove expedient to add individual reactants during the reaction. For example, you can add ZrCl4 or HfCl4 during the reaction to control the reaction rate and thus the heat of reaction.
  • the reaction mixture is generally deactivated with water or an ice / water mixture, which may or may not have been acidified.
  • the mixture is then usually filtered in order to separate Al metal or undissolved reaction components. A phase separation may still be necessary.
  • the aqueous phase obtained is then optionally extracted with a polar, organic solvent, for example with chloroform or dichloromethane, in order to give unreacted compounds or valuable by-products remove.
  • This extraction stage is of particular interest if the reaction variant in which (R) 2M (Hal) 2 is formed is selected.
  • the mixture is generally deactivated with acidified water or an ice / water mixture and, after the filtration and phase separation, the extraction is carried out with an organic, polar solvent.
  • the compound of formula I is initially obtained in the form of the halide. This is optionally isolated and purified in a manner known per se, for example by recrystallization, or other anions are introduced in a manner known per se when the reaction mixture is worked up. For example, an acid or a water-soluble salt of said acid can be added to the isolated aqueous phase and the compound of the formula I can be precipitated in this way.
  • Suitable precipitants are the Na or K salts or the free acids of the anions listed above as preferred.
  • the compounds of formula I with non-nucleophilic anions can be used as photoinitiators for cationically polymerizable materials.
  • the compounds of formula I with nuceophilic anions can be used in the manner described above for the preparation of these photoinitiators.
  • Example 1 ( ⁇ 6-mesitylene) - ( ⁇ 5-cyclopentadienyl) iron (II) hexafluorophosphate
  • ferrocene 10 g (0.043 mol) of zirconium tetrachloride and 1.2 g (0.043 mol) of aluminum powder in 50 ml (0.43 mol) of mesitylene are at 60 ° C under N2 within 30 g. 10 g (0.043 mol) of zirconium tetrachloride were added. After heating the reaction mixture to 100 ° C.
  • the mixture is cooled and a solution of 16 ml of 32% HCl in 85 ml of water is slowly added dropwise. After 15 minutes, the mixture is filtered through Hyflo (filter aid), the two phases are separated and the aqueous phase is added to a solution of 8.7 g (0.047 mol) of KPF6 in 100 ml of water.
  • Example 2 A mixture of 8 g ferrocene (0.043 mol), 9 g ZrCl4 (0.0386 mol), 0.6 g AlCl3 (0.0043 mol), 50 ml mesitylene (0.43 mol) and 1 2 g of Al powder (0.043 mol) at 60 ° C before (under N2), and then 10 g (0.043 mol) of ZrCl4 are slowly added at 60 ° C. The reaction mixture is heated to 100 ° C. and kept at this temperature for 2 hours. After working up as in Example 1, 13.6 g of crude ( ⁇ 6-mesitylene) - ⁇ 5- (cyclopentadienyl) iron (II) PF6 (81.9% of theory) mp.
  • Example 3 A mixture of 8 g ferrocene (0.043 mol), 5.7 g AlCl3 (0.043 mol) and 60 ml mesitylene (0.5 mol) at 60 ° C. under N2. Then 2 g (0.0086 mol) of ZrCl4 are added at this temperature within 30 minutes. The mixture is heated to 100 ° C for 2 hours. The mixture is cooled and a mixture of 60 ml dichloromethane and 15 ml 32% HCl solution is added dropwise. Then another 200 ml of water are added and filtered.
  • Example 4 A mixture of 8 g of toluene-crystallized ferrocene (0.043 mol), 5.7 g of sublimed AlCl3 (0.043 mol) and 60 ml of sodium distilled mesitylene (0.5 mol) at 60 ° C. under argon.
  • Example 6 Analogously to Example 5, a stirred mixture of 56 g of cumene, 5 g (0.027 mol) of ferrocene, 4.8 g (0.0358 mol) of aluminum chloride and 0.12 g (0.0045 mol) of aluminum powder is added under nitrogen 4.3 g (0.0134 mol) of hafnium tetrachloride were added at 55 ° C. in the course of 30 minutes. Working up is carried out analogously to Example 4. This gives 3.5 g of hafnocene dichloride (68.6% of theory; mp. 228-230 ° C). UV spectrum in CHCl3: ⁇ max ( ⁇ ) 266.4 nm (2.751) 306.3 nm (0.714) analysis Ber.
  • Example 7 Analogously to Example 4, a stirred mixture of 60 ml of mesitylene, 8 g of ferrocene (0.043 mol) and 5.7 g of sublimed AlCl3 (0.043 mol) under argon at 60 ° C. within 1 hour 10 min. 10 g 0.043 mol) ZrCl4 added. Working up is carried out analogously to Example 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Claims (13)

  1. Procédé de préparation de composés de formule (I)
    Figure imgb0007
     dans laquelle R est un anion de formule C₅H₄R¹ ou C₉H₇, R¹ est un hydrogène, un alkyle en C₁-C₆ ou un halogène,
    R² représente un arène π, X est un anion de valence q et q signifie 1,2 ou 3,
       par réaction du ferrocène ou d'un de ses dérivés (C₅H₄R³)Fe(C₅H₄R¹) ou (C₉H₇)₂Fe, où R³ possède l'une des significations de R¹, avec au moins une mole d'un arène π R², puis éventuellement échange de l'anion Xq- de façon connue en soi, la réaction du ferrocène ou de son dérivé étant effectuée en présence de
    a) au moins 1,2 mole d'un mélange de trihalogénure d'Al et de tétrahalogénure de Zr-IV ou de Hf-IV, éventuellement en présence d'un agent réducteur métallique, le tétrahalogénure de Zr-IV ou de Hf-IV étant présent en une quantité d'au moins 0,2 mole et le trihalogénure d'Al en une quantité d'au moins 0,1 mole,
       ou la réaction du ferrocène ou de son dérivé étant effectuée en présence de
    b) au moins 1,0 mole d'un tétrahalogénure de Zr-IV ou de Hf-IV en tant que seul acide de Lewis en combinaison avec au moins 1,0 mole d'un agent réducteur métallique,
       les quantités indiquées se rapportant toujours à une mole de ferrocène ou de son dérive.
  2. Procédé selon la revendication 1, dans lequel R est un anion cyclopentadiényle C₅H₄R¹.
  3. Procédé selon la revendication 1, dans lequel R¹ est l'hydrogène.
  4. Procédé selon la revendication 1, dans lequel l'arène π R² est un hydrocarbure aromatique de 6 à 24 atomes de carbone ou un hydrocarbure hétérocyclique aromatique ayant 3 à 30 atomes de carbone et un à deux hétéroatomes.
  5. Procédé selon la revendication 1, dans lequel Xq- est choisi dans le groupe constitué par BF₄⁻, PF₆⁻, AsF₆⁻ et SbF₆⁻.
  6. Procédé selon la revendication 1, dans lequel le tétrachlorure de Zr-IV ou de Hf-IV est ZrCl₄ ou HfCl₄ et dans lequel le trihalogénure d'Al représente AlCl₃, en particulier AlCl₃ sublimé.
  7. Procédé selon la revendication 1, dans lequel la quantité totale d'acide de Lewis dans la variante a) est de 1,2 - 4,0 moles et dans la variante b) de 1,0 - 3,0 moles, rapportée à une mole de ferrocène ou de son dérivé.
  8. Procédé selon la revendication 1, dans lequel le rapport molaire du tétrahalogénure de Zr-IV ou de Hf-IV au trihalogénure d'Al dans la variante a) est de 1:4 à 4:1.
  9. Procédé selon la revendication 1 pour la préparation simultanée de composés de formule I et de formule III
    Figure imgb0008

            (R)₂M\(Hal)₂   (III),



    dans lesquelles M représente Zr ou Hf, Hal est un atome d'halogène et R, R², X et q ont la signification définie dans la revendication 1, caractérisé en ce que l'on utilise un mélange de tétrahalogénure de Zr-IV ou de Hf-IV/trihalogénure d'Al contenant 0,3 - 0,7 mole de l'halogénure-IV correspondant, pour une mole de ferrocène ou de son dérivé, en combinaison avec un agent réducteur métallique.
  10. Procédé selon la revendication 9, dans lequel on utilise un mélange de 0,3 - 0,7 mole de tétrahalogénure de Zr-IV ou de Hf-IV et de 0,8 - 2,0 mole de trihalogénure d'Al pour une mole de ferrocène ou de son dérivé, avec de l'Al finement divisé, et dans lequel l'halogénure représente un bromure ou un chlorure.
  11. Procédé selon la revendication 9, dans lequel on utilise un mélange de 0,4 - 0,6 mole de tétrahalogénure de Zr-IV ou de Hf-IV et de 1,0 - 1,8 mole de trihalogénure d'Al, avec 0,1 - 1,0 mole d'Al finement divisé, pour une mole de ferrocène ou de son dérivé, et dans lequel l'halogénure représente un bromure ou un chlorure.
  12. Procédé selon la revendication 9, dans lequel on utilise comme acide de Lewis un mélange de 0,4 - 0,6 mole de ZrCl₄ ou de HfCl₄ et de 1,2 - 1,4 mole d'AlCl₃, avec 0,15 - 0,2 mole d'Al finement divisé, pour une mole de ferrocène ou de son dérivé.
  13. Procédé selon la revendication 9, dans lequel on désactive le mélange réactionnel après la fin de la réaction avec de l'eau acidifiée ou un mélange d'eau/glace acidifié et on extrait avec un solvant organique polaire la phase aqueuse obtenue après filtration et séparation de phases.
EP88810710A 1987-10-26 1988-10-18 Procédé pour la préparation de composés organométalliques Expired - Lifetime EP0314618B1 (fr)

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Cited By (1)

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US6255507B1 (en) 1998-09-18 2001-07-03 3M Innovative Properties Company Process for preparing cyclopentadienyliron (II) arene complex

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US5247107A (en) * 1987-10-26 1993-09-21 Ciba-Geigy Corporation Process for the preparation of organometallic compounds
US5074201A (en) * 1989-05-12 1991-12-24 Matsushita Electric Industrial Co., Ltd. Apparatus for manufacturing tonyu and tofu
US5059701A (en) * 1990-09-20 1991-10-22 Minnesota Mining And Manufacturing Company Methods for preparation of cyclopentadienyliron (II) arenes
WO1993010483A1 (fr) * 1991-11-12 1993-05-27 University Of Georgia Research Foundation, Inc. Photoinitiation anionique
US5652280A (en) * 1991-11-12 1997-07-29 University Of Georgia Research Foundation, Inc. Anionic photoinitiation
US5922783A (en) 1997-02-27 1999-07-13 Loctite Corporation Radiation-curable, cyanoacrylate-containing compositions
US20050059752A1 (en) 2002-07-12 2005-03-17 Rhodia Chimie Stable, cationically polymerizable/crosslinkable dental compositions having high filler contents
JP4606229B2 (ja) * 2005-04-07 2011-01-05 ダイセル化学工業株式会社 シクロペンタジエニル鉄（ｉｉ）アレーンカチオン錯塩又はその類縁体の製造法
CN101587089B (zh) * 2008-05-23 2012-11-28 中国科学院大连化学物理研究所 二茂铁-多孔金属有机骨架化合物复合材料及制备和应用

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EP0094915B1 (fr) * 1982-05-19 1987-01-21 Ciba-Geigy Ag Compositions durcissables à base de complexes métallocènes, obtention de précurseurs activables et emploi

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Publication number Priority date Publication date Assignee Title
US6255507B1 (en) 1998-09-18 2001-07-03 3M Innovative Properties Company Process for preparing cyclopentadienyliron (II) arene complex

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CA1328275C (fr) 1994-04-05
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EP0314618A3 (en) 1990-08-29
DE3889067D1 (de) 1994-05-19
JPH01146889A (ja) 1989-06-08

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